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Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application

A technology of manganese complexes and catalysts, which is applied in the field of catalyst compositions, can solve the problems of unsuitability for large-scale industrial production, excessive use of additives, and low activity of manganese catalysts, so as to improve catalytic activity and substrate applicability with low cost , the effect of a wide range of substrate application

Active Publication Date: 2021-07-30
HEBEI AGRICULTURAL UNIV.
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Compared with the traditional synthetic method, the research on the preparation of quinoline or pyridine nitrogen heterocycle by ADC reaction is in its infancy, and the main problems include: the activity of manganese catalyst is low (2.0~5.0mol%), which is not suitable for large-scale Industrialized production; most of the high-efficiency catalysts used are based on ruthenium and iridium precious metals (0.025-1.0mol%), which have potential pollution, toxicity and high production costs; the reaction conditions are relatively harsh, the reaction temperature is higher than 130 ° C, and too many additives are used , limiting the industrial application of some processes

Method used

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  • Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application
  • Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application
  • Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application

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Experimental program
Comparison scheme
Effect test

preparation example Construction

[0048] Using a similar preparation method and molar ratio to L1 in Example 1, 3.50 g of L2 was obtained as a yellow oil with a yield of 70%.

[0049] The structural confirmation data are as follows:

[0050] 1 H NMR (CDCl 3 ,400MHz)δ8.30(dd,J=4.8,1.6Hz,1H),7.30(dd,J=7.7,1.6Hz,1H),6.99(dd,J=7.7,4.7Hz,1H),5.18(s ,1H,NH),3.78(dd,J=8.1,5.4Hz,1H),2.82–2.65(m,4H),2.65–2.58(m,2H),2.52 (q,J=7.1Hz,4H), 2.16–2.07(m,1H),1.98–1.90(m,1H),1.81–1.60(m,2H),0.97(t,J=7.1Hz,6H,CH 3 ); 13 C NMR (CDCl 3,100MHz) δ156.51, 146.77, 136.97, 132.52, 122.00, 57.83, 52.30, 46.88, 44.38, 28.72, 28.18, 19.77, 11.38.

[0051] The crude product L2 can be acidified by adding 10 mL of 10w% HCl aqueous solution, and further purified to obtain 4.85 g of light yellow solid ligand hydrochloride, with a total yield of 68%.

[0052] The structural confirmation data are as follows:

[0053] 1 H NMR (D 2 O, 400MHz) δ8.54 (d, J = 5.2Hz, 1H), 8.13 (d, J = 7.9Hz, 1H), 7.71 (ddt, J = 7.8, 5.1, 2.6Hz, 1H), 4.58 (d...

Embodiment 4

[0062] Example 4 Preparation of 2-(ethylthio)ethylamine

[0063]

[0064] Under nitrogen atmosphere, 11.3g (0.10mol) 2-chloroethylamine hydrochloride, 4.0g (0.10mol) NaOH and 4.6g (0.20mol) LiOH were put into 120mL EtOH and 30mL H 2 O in a 250mL single-necked bottle. After the mixture was stirred at 0°C for 10 minutes, 11.8 g (110 mmol) of bromoethane was added dropwise to the mixture keeping the temperature below 5°C. After the addition, the system was slowly warmed up to 35°C and continued to stir for 24 hours. GC detected that the reaction was complete. After removing a large amount of inorganic salts by filtration, the filtrate was spin-dried to remove a large amount of ethanol. To the concentrate was added 40 mL of water and extracted with dichloromethane (3 x 60 mL). Organic phase with or without NaSO 4 Dry and concentrate under reduced pressure to obtain 6.5 g of yellow oil 2-(ethylthio)ethylamine with a yield of 61%.

[0065] The structural confirmation data are...

Embodiment 11

[0098] Example 11 The compound Mn-4 represented by formula 1 catalyzes the dehydrogenation coupling of ampicol (1a) and cycloheptanone (2a) into 7,8,9,10-tetrahydro-6H-cyclohepta[b]quinoline (3aa)

[0099] in N 2 Under atmosphere, put 61mg (0.5mmol) o-aminobenzyl alcohol, 112mg (2eq., 1.0mmol) cycloheptanone, 4.5mg (10umol, 2mol%) Mn-4, 1.0mmol (2eq.) base promoter into 20mL Schlenk bottle, and add a certain amount (2.0 ~ 4.0mL) toluene and (0.5 ~ 1.0mL) tetrahydrofuran. The reaction mixture was stirred at 120°C for 48-72 hours. Cool to room temperature, add 5 mL saturated NH 4 The Cl aqueous solution was detected and analyzed by GC (using mesitylene as an internal standard) and the results are shown in Table 1.

[0100]

[0101] Table 1: Results of 3aa prepared by dehydrocoupling reaction under different cocatalysts a .

[0102]

[0103]

[0104] a Reaction conditions: 0.5mmol o-aminobenzyl alcohol, 1.0mmol cycloheptanone, 10umol Mn-4, 1.0mmol base additive, 4...

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Abstract

The invention discloses a pincerlike manganese complex, a preparation method thereof, a ligand for preparation, a preparation method of the ligand, a catalyst composition taking the complex as an active component and application of the catalyst composition. According to the pincerlike manganese complex, a cycloalkyl ring is introduced into a ligand framework, and by regulating and controlling the cyclic tension, flexibility and steric hindrance of the cycloalkyl ring, the reactivity and stability of the manganese metal center can be effectively adjusted, and the catalytic activity and substrate applicability of a manganese metal system are remarkably improved. The catalyst composition taking the pincerlike manganese complex as an active component has the advantages of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of preparing quinoline or pyridine derivatives by catalyzing dehydrogenation coupling reaction of o-amino aromatic alcohol or gamma-amino alcohol, ketone or secondary alcohol; and the synthesis advantages of low cost and stable performance are embodied, the operation is simple, and the yield is high.

Description

technical field [0001] The invention relates to a pincer-shaped manganese complex, a preparation method thereof, a preparation ligand and a preparation method, a catalyst composition with the complex as an active component, and an application thereof. Background technique [0002] Quinoline and pyridine derivatives have important physiological and pharmaceutical activities, and are widely demanded in the fields of medicine, agriculture, functional materials, and catalytic reactions. Some important drugs (Mini Rev Med Chem 2009, 9, 1655; J. Med. Chem. 2020, 63, 10652), such as the antipsychotic drug Blonanserin, the ALK inhibitor Lorlatinib Both Bosutinib and Bosutinib for the treatment of leukemia contain pyridine or quinoline structural units. Therefore, many classic synthetic methods (Tetrahedron 2004, 60, 6043-6061; Chem. Eur. J. 2010, 16, 12052; Chem Rev 2009, 109, 2652-2671) were developed for the preparation of quinolines or pyridines derivative. However, these meth...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F13/00C07D215/40B01J31/20C07D213/22C07D213/26C07D213/30C07D215/06C07D219/02C07D219/04C07D221/04C07D221/10C07D221/16C07D221/18C07D401/04C07D405/04C07D409/04C07D471/04C07D471/18
CPCC07F13/00C07D215/40B01J31/20C07D221/16C07D221/18C07D471/04C07D471/18C07D405/04C07D409/04C07D219/02C07D401/04C07D219/04C07D221/04C07D215/06C07D221/10C07D213/22C07D213/30C07D213/26B01J2531/72B01J2231/4283B01J2231/4205B01J2231/763B01J2231/766
Inventor 王征刘笑颖李立斌马宁韩鹏杜兰星张新颖吕世松
Owner HEBEI AGRICULTURAL UNIV.
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